IP Library Granted Patent US 12,427,758
Granted Patent B2
US 12,427,758 · App. 18/759,323 · Granted Sep 30, 2025

Multi-layer film with improved modulus properties

Inventors: Heinz Pudleiner (Krefeld, DE); Klaus Meyer (Dormagen, DE); Jürgen Winkler (Langenfeld, DE); Wolfgang Brauer (Leverkusen, DE); Joerg Nickel (Dormagen, DE); Craig Pehlert (Lenox, MA); Chunhua Li (Cupertino, CA); Yan Chen (Cupertino, CA)
Assignee: Covestro Intellectual Property GmbH & Co. KG
B32B27/08A61C5/007A61C13/0022B29C48/0011B29C48/0017B29C48/08B29C48/21B29C48/625B29C48/92B32B27/36B32B27/365B32B27/40C08J7/042C08L75/08B29C48/30B29C48/34B29C2948/92609B29C2948/92704B32B2250/03B32B2250/24B32B2250/40B32B2307/4026B32B2307/412B32B2307/536B32B2307/54B32B2535/00C08J2369/00C08J2467/02C08J2475/04Y10T428/24967Y10T428/24983
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Quick Facts
Patent No.
US 12,427,758
App. No.
18/759,323
Granted
Sep 30, 2025
Kind
B2
Abstract

The invention relates to a multi-layer, preferably co-extruded, plastic film with improved modulus properties, which is suitable, in particular, for producing three-dimensionally shaped articles.

Claims (55)

1. A multi-layer plastic film, having

a layer A consisting of an at least one copolyester, the layer A having a glass transition temperature T g from 80° C. to 200° C.,

and at least one layer B containing at least one thermoplastic polyurethane, the at least one layer B exhibiting a hardness from 45 Shore D to 85 Shore D,

and at least one third layer containing at least one polycarbonate or copolycarbonate and/or at least one polyester or copolyester,

wherein the tensile strength of the multi-layer plastic film is in the range of from 40 to 60 N/mm 2 , determined in accordance with ASTM D 638.

2. The multi-layer plastic film according to claim 1 , wherein the layer A exhibits an inherent viscosity from 0.50 dL/g to 1.20 dL/g and a glass transition temperature T g from 80° C. to 200° C.

3. The multi-layer plastic film according to claim 1 , wherein the at least one layer B contains at least one thermoplastic polyurethane exhibiting a hardness from 45 Shore D to 85 Shore D.

4. The multi-layer plastic film according to claim 1 , wherein

the layer A consisting of the at least one copolyester exhibits residues from

(a) a dicarboxylic acid component comprising

i) 70 mole % to 100 mole % terephthalic acid residues,

ii) 0 mole % to 30 mole % aromatic dicarboxylic acid residues with up to 20 carbon atoms, and

iii) 0 mole % to 10 mole % aliphatic dicarboxylic acid residues with up to 16 carbon atoms, and

(b) a diol component comprising

i) 5 mole % to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and

ii) 50 mole % to 95 mole % 1,4-cyclohexanedimethanol residues,

wherein the sum of the mole % of residues i)-iii) of the dicarboxylic acid component amounts to 100 mole % and the sum of the mole % of residues i) and ii) of the diol component amounts to 100 mole %, and

wherein the inherent viscosity of the at least one copolyester amounts to 0.50 dL/g to 1.20 dL/g and the at least one copolyester exhibits a glass transition temperature T g from 80° C. to 150° C.,

and the layer A is located next to the at least one layer B containing at least one thermoplastic polyurethane, the thermoplastic polyurethane exhibiting a hardness from 45 Shore D to 85 Shore D and being obtainable from

a) one or more linear polyether diols with mean molecular weights from 500 g/mol to 10,000 g/mol, and, on average, in each instance at least 1.8 and at most 3.0 Tserevitinov-active hydrogen atoms

b) one or more organic diisocyanates,

c) one or more diol chain-extenders with molecular weights from 60 g/mol to 500 g/mol and with, on average, 1.8 to 3.0 Tserevitinov-active hydrogen atoms

in the presence of

d) optionally, one or more catalysts

with addition of

e) optionally, auxiliary substances and additives,

wherein the molar ratio of the NCO groups in b) to the groups in a) and c) that are reactive towards isocyanate amounts to 0.85:1 to 1.2:1.

5. The multi-layer plastic film according to claim 4 , wherein the one or more linear polyether diols have mean molecular weights from 500 g/mol to 6000 g/mol.

6. The multi-layer plastic film according to claim 4 , wherein the one or more linear polyether diols have, on average, in each instance 1.8 to 2.2, Tserevitinov-active hydrogen atoms.

7. The multi-layer plastic film according to claim 4 , wherein the molar ratio of the NCO groups in b) to groups in a) and c) that are reactive towards isocyanate amounts to 0.9:1 to 1.1:1.

8. The multi-layer plastic film according to claim 4 , wherein the one or more polyether diols are based on one or more units selected from the group consisting of 1,4-butanediol units and 1,3-propylene glycol units.

9. The multi-layer plastic film according to claim 4 , wherein the one or more organic diisocyanates are one or more selected from the group consisting of 4,4′-diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, and 1,6-hexamethylene diisocyanate.

10. The multi-layer plastic film according to claim 4 , wherein the one or more diol chain-extenders are one or more selected from the group consisting of 1,4-butanediol, 1,3-propanediol, 1,2-propanediol, 1,2-ethylene glycol, 1,6-hexanediol, 1,4-di(β-hydroxyethyl) hydroquinone, and 1,4-di(β-hydroxyethyl)bisphenol A.

11. The multi-layer plastic film according to claim 4 , wherein the thermoplastic polyurethane was produced in a prepolymer process.

12. The multi-layer plastic film according to claim 4 , wherein the diol component of the at least one copolyester comprises 10 mole % to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 65 mole % to 90 mole % 1,4-cyclohexanedimethanol residues, the sum of the mole % of these two components of the diol component amounting to 100 mole %.

13. The multi-layer plastic film according to claim 12 , wherein the diol component of the at least one copolyester comprises 15 mole % to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 65 mole % to 85 mole % 1,4-cyclohexanedimethanol residues, the sum of the mole % of these two components of the diol component amounting to 100 mole %.

14. The multi-layer plastic film according to claim 12 , wherein the diol component of the at least one copolyester comprises 15 mole % to 30 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 mole % to 85 mole % 1,4-cyclohexanedimethanol residues, the sum of the mole % of these two components of the diol component amounting to 100 mole %.

15. The multi-layer plastic film according to claim 4 , wherein the dicarboxylic acid component comprises 95 mole % to 100 mole % terephthalic acid residues.

16. The multi-layer plastic film according to claim 2 , wherein the at least one copolyester exhibits an inherent viscosity from 0.50 dL/g to 0.80 dL/g.

17. The multi-layer plastic film according to claim 1 , wherein the at least one copolyester exhibits a glass transition temperature T g from 85° C. to 130° C.

18. The multi-layer plastic film according to claim 17 , wherein the at least one copolyester exhibits a glass transition temperature T g from 90° C. to 120° C.

19. The multi-layer plastic film according to claim 1 , wherein the at least one thermoplastic polyurethane exhibits a hardness from 50 Shore D to 80 Shore D.

20. The multi-layer plastic film according to claim 1 , wherein the film has been co-extruded.

21. The multi-layer plastic film according to claim 1 , wherein the film has a total thickness from 300 μm to 2000 μm.

22. The multi-layer plastic film according to claim 21 , wherein the film has a total thickness from 400 μm to 1500 μm.

23. The multi-layer plastic film according to claim 21 , wherein the film has a total thickness from 500 μm to 1200 μm.

24. The multi-layer plastic film according to claim 1 , wherein the layer A has a layer thickness from 250 μm to 1600 μm.

25. The multi-layer plastic film according to claim 24 , wherein the layer A has a layer thickness from 350 μm to 1400 μm.

26. The multi-layer plastic film according to claim 24 , wherein the layer A has a layer thickness from 400 μm to 1000 μm.

27. The multi-layer plastic film according to claim 1 , wherein the at least one layer B has a layer thickness from 25 μm to 500 μm.

28. The multi-layer plastic film according to claim 27 , wherein the at least one layer B has a layer thickness from 30 μm to 300 μm.

29. The multi-layer plastic film according to claim 27 , wherein the at least one layer B has a layer thickness from 50 μm to 200 μm.

30. The multi-layer plastic film according to claim 1 , wherein the film has a tensile modulus in the range of from 1000 to 1300 N/mm 2 .

31. The multi-layer plastic film according to claim 1 , wherein layer A and the third layer are made from the same material.

32. A three-dimensionally shaped article obtained by three-dimensionally forming the multi-layer plastic film according to claim 1 .

Assignments (5)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 6, 2024
From: LI, CHUNHUA; CHEN, YAN
To: ALIGN TECHNOLOGY INC.
Reel/Frame 068190/0960 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 6, 2024
From: PUDLEINER, HEINZ; MEYER, KLAUS; WINKLER, JUERGEN; BRÄUER, WOLFGANG; NICKEL, JOERG; PEHLERT, CRAIG
To: BAYER MATERIALSCIENCE AG
Reel/Frame 068192/0392 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 6, 2024
From: ALIGN TECHNOLOGY INC.
To: COVESTRO DEUTSCHLAND AG
Reel/Frame 068193/0430 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 6, 2024
From: COVESTRO DEUTSCHLAND AG
To: COVESTRO INTELLECTUAL PROPERTY GMBH & CO. KG
Reel/Frame 068338/0893 →
CHANGE OF NAME Recorded Aug 6, 2024
From: BAYER MATERIALSCIENCE AG
To: COVESTRO DEUTSCHLAND AG
Reel/Frame 068866/0001 →
Continuity (6)
Continuation 18200295 · May 22, 2023
Continuation 17847468 · Jun 23, 2022
Continuation 17094182 · Nov 10, 2020
Continuation 16224867 · Dec 19, 2018
Continuation 14400363
Related Publication 20240351317A1 · Oct 24, 2024
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